Novel photographic products, processes and compositions employing anthraquinone dye developers



ferred to as United States Patent This invention relates to photography and more particularly to products, compositions and processes for the development of photosensitive silver halide elements.

It is one object of the present invention to provide novel processes and compositions for the development of silver halide emulsions, in which novelcolored developing agents are used.

Another object is to provide novel processes and compositions for the development of silver-halide emulsions,

in which the novel developing agent is capable of devel-' oping an exposed silver halide emulsion reversed or positive colored image of the developed image to a superposed image-receiving material;

A further object is to provide novel silver halide developing agents and novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images.

Other objects and will in part appear hereinafter.

The invention accordingly comprises theprocesses involving the several steps and the relation and order of one or more of such steps with respect to each of'the others, and the products and compositions possessing the features, properties and therelation of elements which are exemplified in the following detailed disclosure, and the scope of the applications of which will be indicated in the claims.

The objects of this invention may be accomplished by the use of certain novel dyes which have the ability to develop images present in an exposed silver halide emulsion; thus they may be referred to as dye developers. These novel dyes or dye developers will be further described hereinafter.

For a fuller understanding of the nature and objects of,

-the invention, reference should be had to the following 1 detailed description.

The photographic processes'and compositions disclosed herein are particularly useful in the treatment of an exposed silver halide emulsion, whereby at'positive dyeimage maybe imparted toanother element, herein rean image-carrying or image-receiving element.

U. S. Patent No. 2,983,606, issuedMay 9, 1961, to Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative .material, such as a pho tographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer'a reversed or positive dye image of the developed'im'age by permeating into said emulsion a suitable liquid processing composition and I bringing-said emulsion into superposed relationship with an appropriate image-receiving layer. The-inventive concepts herein set forth use in such processes.

In carrying out the process of this invention, a photosensitive -element containing a silver halide emulsion is providenovel dye developers for exposed and wetted with a liquid processing composition,

for example by immersing, coating, spraying, flowing, etc{, in the dark, and the prior to, during or after wetting, on an image-receiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid 7 Cambridge, Mass., acorporation solubility in alkaline solutions.

of the invention will in part be obvious photosensitive element superposed 3 processing composition is applied to the photosensitive element in a uniformlayer as the photosensitive element s brought into superposed position with an image-receivmg'element. The .liquid processing composition per-- 5 meates'the emulsion toprovide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in'situ with the developed silver, thereby pro- 1 viding an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due,- at least in part,

- to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. At-least part of this imagewise distribution'o'f unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. The

Patented Apr. 28, 1964 image-receiving layer receives a depthwise diffusion, from and imparting a Ithe'emulsion, of unoxidized dye developer, without appreciably disturbing theimagewise distribution thereof, to provide a reversed or positive, colored image of the developed or negative image' The image-receiving ele- \ment may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. lmbibition periods of approximately one minute have been found to give good results, but this contact periodmay be adjusted where necessary to compensate for variations in 3 0 temperature or other conditions. The desired positive image is revealed by stripping the image-receiving layer from the, silver halide emulsion at' the end of the imbibition period.

The dye developers of this invention may be utilized '35 in the photosensitive element, for example in, on orbehind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In-a'preferred embodiment, a coating or layer I of the dye developer is placed behind the silver halide 40 emulsion, i.e., on the side of the emulsion adapted to be located most distant from. the photographed subject when the emulsion is exposed and preferably also adapted to be most distant ,from the image-receiving layer when in superposed relationship therewith. Placing the dye developer' behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any light-filtering action by the colored dye developer. In

be applied by using a coating solution containing about 0.5 to 8%, by weight, ofthe dye developer. Similar concentrations may be used if the dye developer is utilized as a component-of the liquid processing composition. In an especially 'useful mode of disposing the dye developers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed in a gelatincoating solution. i The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, di-

ethylamine, sodium hydroxide or sodium carbonate, and

contain an additional silver halide developing agent. If the liquid processing composition is to he applied to the emulsion byb eing spread thereon, preferably in a rela- -tively thin, uniform layer, it may also include a viscosityincreasing compound constituting film-forming material of the typewhich, when spread over a water-absorbent base, will form a relatively firm and relatively stable film.v A preferredfilm-forming material is a high molecthis preferred embodiment, the layer of dye developer may,

may contain thedye developer. In some instances, it may ular weight polymer such as apolymeric, water-soluble ether inert to an alkali solution,

as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used. The novel dye developers. of this invention are amino or hydroxy-substituted anthraquinone dyes having bonded directly to the 2,3 carbon atoms of the anthraquinone nucleus, a substitucnt of the formula:

wherein: Y is a dihydroxyphenyl silver halide developing radical, e.g., p-dihydroxyphenyl, odihydroxyphenyl and halogen and alkyl substituted derivatives thereof; X is a divalent radical or a covalent bond; and each of R and R may be hydrogen or a lower alkyl radical; said substituent being bonded to said nuclear carbon atoms through said radicals, e.g., one of said wherein: Y has the meaning heretofore noted and X is a lower alkylene radical.

In addition to containing an amino and/or hydroxy radical and the substituent of Formula A or B, it is contemplated that the anthraquinone nucleus may also contain other substituents. As examples of additional substituents which may be bonded'to a nuclear carbon atom of the anthraquonone nucleus, mention may be made of lower alkyl groups; an aryl group, e.g., phenyl; an acyl group, e.g., an acetyl radical; a halo group, such as chlorine; or a sulfo group. It is to be understood that the expressions alkyl," aryl and amino include substituted derivatives thereof, i.e., they may be further substituted by suitable alkyl, aryl, or acyl radicals, e.g., alkylamino, acylamino, aminoalkyl, etc.

The expression divalent radical" as used herein is intended to include divalent organic, divalent inorganic and divalent organic radicals containing hetero groups as constituent components of said radicals.

In the preferred embodiment of the invention, Y is a p-dihydroxyphenyl group; X is a lower alkylene group, as heretofore noted, and an hydroxy and/ or primary amino group is substituted at positions 1 and 4 on the anthraquinone nucleus.

The preferred compounds of this invention may be represented by the following formula:

K 5 Z Y l 0 O OH wherein X is a lower alkylene radical, and each Z is hydroxy or amino and may be the same or different.

As an example of a dye developer within the class comprising the preferred embodiment of the invention, mention may be made of:

1,4-dlamlno-N-(IS-2,5-dthydroxyphenyl-a-methyl-ethyl) 2,3- anthraqutnone-dtearboxamlcle As an example of another dye developer within the scope of this 1nvention, mention may be made of the following:

l-amino-hydroxy-N 5-2,5'-dlhydroxyphenyl-a-methylethyl) -2,3-anthraquinone-dicarboxnmlde wherein Y, X, R and R have the same meaning as above.

Among the preferred divalent organic radicals signified by the term X in the above formulae, mention may be made of alkylene radicals, such as ethylene, propylene, etc., arylene radicals, such as p-phenylene, alkarylene radicals, such as -'-on,-orr

and acyl radicals, such as It is to be understood that the expressions alkylene," arylene and alkarylene include substituted derivatives thereof, i.e., they may be further substituted by suitable alkyl radicals, such as methyl, ethyl, etc., aryl radicals, sugh als a phenyl radical, or acyl radicals, such as an acetyl ra ica V The preferred compound within the groupfrepresented by Formula D is:.

(E) on CH -(fH-CH; NH:

on a

2- (fi amin'o-propyl) -hydroquinone ing light-sensitive materials are carried fl-Aminoethyl-hydroquinone and fi-amino-p-ethyl-ethyl hydroquinone may also be used in the preferred emwherein V is an oxy, sulfonyl or thio radical; U is the number of carbon atoms necessary to constitute the desired aliphatic or aromatic configuration; and Y has the same meaning as above. I

As an example of a suitable compound Within the group represented by Formula F, mention may be made of:

fl-amlno-ethyl-thio-hydroquinone The preparation of 2,3-anthraquinone-dicarboximide dyes suitable for use in the practiceof this invention is' disclosed in US. Patent No. 2,628,963, issued February 17, -1953, to Laucius and Speck' and US; Patent No.

2,701,802, issued February 8, 1955, to Boyd., The following example illustrates the preparation of" dye developers within given for purposes of illustration only.

Example 1 is dissolved with stirring in methylCellosolve. A sodium hydroxidesolution (0.013 rnol) is added to the mixture in an atmosphere of nitrogen. The resultant mixture is heated at approximately 100 C. for 9.5 hours in an atmosphere of nitrogen. The mixture is then cooled and acidified dropwise with glacial acetic acid. The resultant precipitate is removed from themixture by washed with methanol and then washed with water. The precipitate is purified by-recrystallization from a methyl Cellosolve/ water mixture. The resultant 1,4-diamino-N-(B-2,5-dihydroxyphenyl a methyl ethyl)-2,3-anthraquinone-dicarboximide [Formula 1], a greenish-blue compound, is soluble in sodium hydroxide, reduces silver halide and melts at 274 to 277 C The absorption spectrum of the compound exhibits a at 674 m in pyridine, e=l5,800.

Elemental analysis of the product as C H O -H O;

filtration,

0, percent I 11, percent N, percent Found h the scope ofthis invention and is' v of acetone and, tetrahydrofuran.

In the following example, all parts are given by weight except where otherwise noted, and all operations invo1v-' sence of actim'c radiation. This example is intended to be illustrative only-of the photographic use of the dye developers and should not be construed as limiting the invention in any way.

A photosensitive element is prepared by coating a gela- I tin-coated film base 'with a' solution containing 3% of 1,4-diamino N (3-2,5-dihydroxyphenyl-a-methyl-eth- H yl)-2,3-anthraquinone-dicarboximide [Formula 1 as pre-' pared in Example 1], in a 4% solution of cellulose ace tate hydrogen phthalate in a'50:50 mixture, by volume,

dried, a silver iodobromideemulsion is applied. This photosensitive element is exposed and processed by spreadingan aqueous liquid processing composition com prising:

Percent Sodium carboxymethyl cellulose 4.0 l-phenyl-S-pyrazolidone 0.2 Sodium hydroxide 2.0 Potassium bromide 0.2

. 5o 1,4-diamino 2,3 7 anthraquinone-dicarboximide (0.005 mol) and 2-(B-amino-propyl)-hydroquinone (0.013 11101):-

between saidphotosensitive element and an image-receiw are brought into superposed ing element as said elements relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 10% Nylon Type F8 -(trade name of E. I. du Pont de Nemours & Co., Wilmington, Delaware, for N-methoxymethyl poylhexamethylene adipamide) in 80% aqueous isopropanol.

image-receiving element is separated and contains a cyan positive dye image of the photographed subject.

As wasv mentioned previously, the compounds of this invention are particularly .useful in photographic products, processes and compositions such as are described and claimed in US. Patent No. 2,983,606. This is quite within a short, reasonable time to form a transfer image of satisfactory density. Stated another way, as far as is known, it was never obvious heretofore that the compounds of the present invention could be utilized to form color images by diffusion transfer, since it was believed that amolecule having four linearly fused rings would be unable to diffuse to the image-receiving element.

' The dye developers of this invention are also useful in integral multilayer photosensitive elements for use in multicolor diffusion transfer processes.

of such photosensitive elements,mention may be made of the photosensitive elements disclosed and claimed in the copending US. application of Edwin H. G. Rogers, Serial No. 565,135, filed February 13, 1956,

Land and Howard wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrange ment of this type comprises a support carrying a redsensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye develoyer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkalipermeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements Within the scope of this invention may be used in roll film units which contain a out in the ab-- After this coating has Afteranimbibition period of approximately one minute,-the

As an example associated with each other that, upon processing, the

photosensitive element may be superposed on the imagereceiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylaminophen01; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl- 3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application'of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black-and-white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1 2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufficient to provide the desired color image and do not depend upon coupling reactions to pro duce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former" or coupler and the oxidized developing agent, as well as so-called autocoupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a. colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of image-receiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in U.S. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxymethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., l-phenyl-S-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W.

Lutes, Serial No. 50,849, filed August 22, 1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in U.S. Patent No. 2,968,554, issused to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

This application is in part a continuation of copending application, Serial No. 678,439, filed August 15, 1957.

Copending U.S. application, Serial No. 232,585, filed concurrently herewith, claims the novel compounds of the present invention.

Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A photographic developer composition comprising an aqueous solvent, an alkaline material soluble therein, an auxiliary silver halide developing agent capable of accelerating development, and a compound selected from the group consisting of amino and hydroxy-substituted anthraquinone dyes having a substituent of hte formula:

wherein: Y is a dihydroxyp'henyl silver halide developing radical; and X is a lower alkylene radical; said substituent being bonded directly to the 2,3 carbon atoms of said anthraquinone nucleus.

2. A novel photographic developer composition as defined in claim 1, wherein said auxiliary developer is a 3-pyrazolidone.

3. A novel photographic developer composition comprising an aqueous alkaline solution, an auxiliary silver halide developing agent capable-of accelerating the developing process and l,4-diamino-N-(fl-2',5'-dihydroxyphenyl-a-methyl-ethyl) -2,3 -anthraquinone -dicarboximide.

4. A novel photographic developer composition comprising an aqueous alkaline solution, an auxiliary silver halide developing agent capable of accelerating the developing process and l-amino-4-hydroxy-N-(B-2',5'-dihydroxyphenyl on methyl-ethyl) 2,3 anthraquinonedicarboxirnide.

5. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support and a compound in a layer on the same side of said support as said silver halide emulsion, said compound being selected from the group consisting of amino and hydroxysubstituted anthraquinone dyes having a substitutent of the formula:

wherein: Y is a dihydroxyphenyl silver halide developing radical; and X is a lower alkylene radical; said substituent being bonded directly to the 2,3 carbon atoms of said anthraquinone nucleus.

6. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support and 1,4 diamino-N-(IS-2',5'-dihydroxyphenyl-a-methyl ethyl) -2,3-anthraquinone-dicarboximide in a layer on the same side of said support as said silver halide emulsion.

7. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support and 1-amino-4-hydroxy-N-(-fl-2f,5'-dihydroxyphlenyl-a-tmethylethyl)-2,3-anthraquinone-dicarboximide in a layer on the same side of said support as said silver halide emulsion.

8. In a process of forming a photographic image in color, the steps which comprise developing an exposed silver halide emulsion in the presence of a compound selected from the group consisting of amino and hydroxysubstituted anthraquinone dyes having a substituent of the formula:

wherein: Y is a dihydroxyphenyl silver halide developing radical; and X is a lower alkylene radical; said substituent being bonded directly to the 2,3 carbon atoms of said anthraquinone nucleus; thereby effecting oxidation of said dye developer in exposed areas and providing in said emulsion a predetermined distribution of unoxidized dye developer; and transferring at least part of said distribution of said unoxidized dye developer by imbibition from said emulsion to an image-receiving element in superposed relationship with said emulsion to impart to said image-receiving element a. reversed, positive dye image of the developed image.

9. The process as defined in claim 8, wherein said dye developer is disposed prior to exposure in a photosensitive element containing said emulsion and a solution containing said dye developer is formed by permeating said photosensitive element with an aqueous alkaline liquid capable of solubilizing said dye developer.

10. The process as defined in claim 9, wherein said liquid is introduced by being spread in a substantially uniform layer between said photosensitive element and said image-receiving element as said elements are brought into superposed relationship.

11. The process as defined in claim 9, wherein said liquid contains a thickener for increasing viscosity and for facilitating the spreading thereof between said photosensitive element and said image-receiving element.

12. The process as defined in claim 8, wherein said dye developer is dissolved in an aqueous alkaline solution prior to application thereof to said exposed emulsion.

13. A process as defined in claim 8, wherein said aqueous alkaline solution contains an auxiliary silver halide developer capable of accelerating development.

14. The process as defined in claim 8, wherein said dye developer is 1,4-diamino N (5-2',5'-dihydroxyphenyl-amethyl-ethyl)-2,3-anthraquinone dicarboximide.

15. The process as defined in claim 8, wherein said dye developer is 1-amino-4 hydroxy N (3-215 '-dihydroxyphenyl-a-methyl-ethyl) -2,3-anthraquinone-dicarboximide.

16. The process which comprises developing an exposed photosensitive silver halide emulsion with an aqueous alkaline solution of a compound selected from the group consisting of amino and hydroxy-substituted anthraquinone dyes having a substituent of the formula:

ll wherein: Y is a dihydroxyphenyl silver halide developing radical; and X is a lower alkylene radical; said substituent being bonded directly to the 2,3 carbon atoms .of said anthraquinone nucleus.

17. The process as defined in claim 16, wherein said dye developer is 1,4-diamino-N-(fl-2',5'-dihydroxyphenyla-methyl-ethyl) -2,3 -anthraquinone-dicarboximide.

18. The process as defined in claim 16, wherein said dye developer is l-amino-4-hydroxy-N-(B-2,5'-dihydroxyphenyl-a-methyl-ethyl) -2,3-anthraquinone-dicarboximide.

19. A process as defined in claim 16, wherein said aqueous alkaline solution contains an auxiliary silver halide developer capable of accelerating development.

No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 131.061 I April 28 I964 Myron S. Simon It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, lines 31 to 39, the formula should appear as shown below instead of as in the patent" O NH '0 (2) OH ll H T 3 cn -c I H O OH O 'OH column 6, lines 33 and 34, for ."poylhexamethylene" read polyhexamethylene column 8 line l8, for "issused" read issued line 42 for "hte" read the column 9 line 1, for "substitutent" read substituent Signed and sealed this 3rd day of November 1964. I

(SEAL) Attest:

ERNEST w. SWIDER I EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

8. IN A PROCESS OF FORMING A PHOTOGRAPHIC IMAGE IN COLOR, THE STEPS WHICH COMPRISES DEVELOPING AN EXPOSED SILVER HALIDE EMULSION IN THE PRESENCE OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF AMINO AND HYDROXYSUBSTITUTED ANTHRAQUINONE DYES HAVING A SUBSTITUENT OF THE FORMULA: 